Use of hydrazide stabilizers for 3-isothiazolones

ABSTRACT

Composition comprising (A) 3-isothiazolone antimicrobial compound and (B) an amount of a second hydrazide compound to stabilize said 3-isothiazolone, and method of stabilizing 3-isothiazolone antimicrobial compound, and method of use to inhibit growth of bacteria, fungi, algae, and yeast at a locus are disclosed.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention concerns the stabilization of 3-isothiazolone compoundsby the incorporation with those compounds of certain hydrazidecompounds.

2. Description of the Prior Art

Isothiazolones have generated high commercial interest as microbicidesto prevent spoilage of certain aqueous and non-aqueous products causedby microorganisms. Isothiazolones are highly effective microbicides (asused herein, "microbicides" includes bactericides, fungicides andalgicides and microbicidal activity is intended to include both theelimination of and the inhibition or prevention of growth of microbialorganisms such as bacteria, fungi and algae); by suitable choice offunctional groups, they are useful in a broad range of applications.However, it has been long recognized that either in storage prior toaddition to the substrate to be treated or after addition, theirefficacy may be decreased because they are not stable under practicalconditions of long-term storage. Means have thus been sought for sometime to improve the stability of isothiazolones.

U.S. Pat. Nos. 3,870,795 and 4,067,878 teach the stabilization ofisothiazolones against chemical decomposition by addition of a metalnitrite or metal nitrate, but teach that other common metal salts,including carbonates, sulfates, chlorates, perchlorates, and chloridesare ineffective in stabilizing solutions of isothiazolones, suchsolutions usually being in water or in an hydroxylic solvent.

U.S. Pat. Nos. 4,150,026 and 4,241,214 teach that metal salt complexesof isothiazolones are useful because they have enhanced thermalstability, while retaining biological activity.

It is known to use certain organic stabilizers for isothiazolones,generally for use situations where metal salts may create problems, suchas corrosion, coagulation of latices, insolubility in non-aqueous media,interaction with the substrate to be stabilized, and the like.Formaldehyde or formaldehyde-releasing chemicals are known asstabilizers, (see U.S. Pat. Nos. 4,165,318 and 4,129,448), as arecertain organic chemicals such as orthoesters (U.S. Pat. No. 4,906,274)and epoxides (U.S. Appln. Ser. No. 194,234).

In certain applications, however, it is desirable to avoid addition oforganic stabilizers by virtue of their volatility, decomposition underhigh heat, higher cost, difficulty in handling, potential toxicity, andthe like. Formaldehyde is a suspected carcinogen, and it is desirablenot to use formaldehyde in applications where contact with human skin orlungs may occur.

In actual use, copper salts, such as copper sulfate, have provedefficacious in the stabilization of isothiazolones. However, coppersalts may be undesirable in effluent streams in such operations as inthe manufacture of stabilized isothiazolones or in their blending into aproduct or the use of that product. Copper salts, especially thechlorides, may contribute to possible corrosion, or in the presence ofpolymers in aqueous dispersion may lead to coagulation of thedispersion.

SUMMARY OF THE INVENTION

It is an object of the invention to provide a stabilization system forisothiazolones which overcomes some or all of the disadvantages of priorart systems. It is also an object to provide an isothiazolone stabilizedby only low levels of stabilizer so as to avoid interference with othercomponents in systems in which isothiazolones are used as microbicides.

These objects, and others which will become apparent from the followingdisclosure, are achieved by the present invention. It has beensurprisingly found that isothiazolones may be stabilized againstdecomposition by the addition of a hydrazide-containing compound to thecomposition containing the isothiazolone. Accordingly the inventionprovides in one aspect a composition comprising:

a) at least one 3-isothiazolone of the formula (I) ##STR1## wherein Y isan unsubstituted or substituted (C₁ -C₁₈) alkyl, an unsubstituted orsubstituted (C₃ -C₁₂) cycloalkyl, an unsubstituted orhalogen-substituted (C₂ -C₈) alkenyl or alkynyl, an unsubstituted orsubstituted (C₇ -C₁₀) aralkyl, or an unsubstituted or substituted aryl;and

R and R¹ is each independently H, halogen or (C₁ -C₄) alkyl; and

b) a hydrazide-containing compound.

In another aspect, the invention comprises a method for inhibiting orpreventing the growth of bacteria, fungi, yeast or algae in a locussubject or susceptible to contamination by bacteria, fungi, yeast oralgae, which comprises incorporating onto or into the locus, in anamount which is effective to adversely affect the growth of bacteria,fungi, yeast, or algae, the aforementioned composition.

DETAILED DESCRIPTION OF THE INVENTION AND THE PREFERRED EMBODIMENTS

The isothiazolones which are stabilized include those disclosed in U.S.Pat. Nos. 3,523,121 and 3,761,488 and represented by the formula##STR2## as defined above. In particular Y may be a (C₁ -C₁₈)alkyl or(C₃ -C₁₂)cycloalkyl each optionally substituted with one or more ofhydroxy, halo, cyano, alkylamino, dialkylamino, arylamino, carboxy,carbalkoxy, alkoxy, aryloxy, alkylthio, arylthio, haloalkoxy,cycloalkylamino, carbamoxy, or isothiazolonyl; and unsubstituted orhalo-substituted (C₂ -C₈) alkenyl or alkynyl; a (C₇ -C₁₀)aralkyloptionally substituted with one or more of halogen, (C₁ -C₄)alkyl or (C₁-C₄)alkoxy; and an aryl optionally substituted with one or more ofhalogen, nitro, (C₁ -C₄)alkyl, (C₁ -C₄)alkyl-acylamino, carb(C₁-C₄)alkoxy or sulfamyl.

Preferred substituents for Y are substituted or unsubstituted (C₁ -C₁₈)alkyl or (C₃ -C₁₂)cycloalkyl; R is preferred to be H, Me or Cl; and R¹is preferred to be H or Cl. Representative of such preferred Ysubstituents are methyl, ethyl, propyl, isopropyl, butyl, hexyl, octyl,cyclohexyl, benzyl, 3,4-dichlorobenzyl, 4-methoxybenzyl, 4-chlorobenzyl,3,4-dichlorophenyl, 4-methoxyphenyl, hydroxymethyl, chloromethyl,chloropropyl, hydrogen, and the like.

Particularly preferred isothiazolones are5-chloro-2-methyl-3-isothiazolone, 2-methyl-3-isothiazolone,2-n-octyl-3-isothiazolone, 4,5-dichloro-2-cyclohexyl-3-isothiazolone and4,5-dichloro-2-octyl-3-isothiazolone.

Most preferred is 5-chloro-2-methyl-3-isothiazolone, either as a solecompound or in admixture with 2-methyl-3-isothiazolone. When inadmixture, the preferred ratio of monochlorinated/unchlorinatedisothiazolone is from about 70:30 to about 85:15, and an especiallypreferred ratio is from about 70:30 to about 80:20. A second especiallypreferred isothiazolone is 2-methyl-3-isothiazolone in combination withlow levels of 5-chloro-2-methyl-3-isothiazolone, a preferred ratio beingfrom about 98:2 to about 96:4, and an especially preferred ratio beingabout 97:3.

Preferred hydrazide-containing compounds are unsubstituted orsubstituted alkyl hydrazides, aryl hydrazides, semicarbazides,heterocyclic hydrazides, and alkyl dihydrazides. Particularly preferredspecific compounds include maleic hydrazide and p-toluic hydrazide.

Some hydrazide-containing compounds are known to have microbicidalactivity, although their efficacy as stabilizers of isothiazolones hasnot previously been appreciated. Such compounds will be particularlydesirable to use as stabilizers; examples are benzyl hydrazide andmaleic hydrazide.

The composition may contain from about 0.01 to about 99.9999 parts ofthe one or more isothiazolones, and from about 0.0001 to about 99.9parts of the hydrazide-containing compound.

Generally, the composition of the invention will be in the form of asolution. Typical formulation ranges are illustrated in the followingTable (all percentages are parts by weight) for both a concentratedsolution of the isothiazolone and a dilute solution. For certain uses,such as shipping of large quantities, more concentrated solutions mayalso be utilized.

    ______________________________________                                        FORMULATIONS TABLE                                                                         Hydrazide-containing                                             Isothiazolone                                                                              Compound       Solvent                                           ______________________________________                                        (I, Supra)   0.0001-99.9%   0-99.9899%                                        0.01-99.9999%                                                                 Preferred     0.01-20%      30-99.89%                                         0.1-50%                                                                       ______________________________________                                    

Solvents may be used to dissolve the isothiazolones and may be anyorganic solvent which dissolves the isothiazolones, is compatible withthe proposed end use, does not destabilize the isothiazolone, and doesnot react with the hydrazide-containing compound to eliminate itsstabilizing action.

Hydroxylic solvents, for example, polyols, such as glycols, alcohols andthe like, may be used. Under conditions of high dilution and high ratiosof stabilizer to isothiazolone, glycols may be successfully used. Incertain formulations, hydrocarbons, either aliphatic or aromatic, areuseful solvents.

Preferred solvents are capped polyols, wherein the free hydroxyl groupis replaced with an ether or ester function. Especially preferred are2,5,8,11 tetraoxadodecane, commonly known as triethylene glycol dimethylether, and 4,7-dioxaundecanol-1 acetate, commonly known as diethyleneglycol butyl ether acetate.

Water is a solvent for certain of the preferred isothiazolones and thehydrazide-containing compound may be employed in aqueous formulations.

The amounts of hydrazide-containing compound employed will varydepending on use conditions and concentrations of the isothiazolone inthe mixture: effective amounts of hydrazide-containing compounds basedon isothiazolone may be ratios in the range of from about 1:100 to about1000:1 stabilizer to isothiazolone. In concentrated solutions, ratiosare generally from about 1:50 to about 50:1. Obviously higher amountsmay be used, but at additional cost. At high levels of dilution of theisothiazolone (such as from 1 to 10,000 ppm isothiazolone in thesolvent), the ratio of stabilizer to isothiazolone can range from about1:10 to about 20:1. The preferred range is from 1:1 to 20:1.

The stabilization advantages of the hydrazide-containing compounds ofthe present invention are noted even when the isothiazolone containsother salt stabilizers recorded in U.S. Pat. Nos. 3,870,795, 4,067,878,4,150,026 and 4,241,214.

Uses of these new organically stabilized microbicides are typically atany locus subject to contamination by bacteria, fungi, yeast or algae.Typically loci are in aqueous systems such as water cooling, laundryrinse water, oil systems such as cutting oils, oil fields and the likewhere microorganisms need to be killed or where their growth needs to becontrolled. However these stabilized microbicides may also be used inall applications for which known microbicidal compositions are useful;preferred utilities of the compositions are to protect wood, paint,adhesive, glue, paper, textile, leather, plastics, cardboard,lubricants, cosmetics, food, caulking, feed and industrial cooling waterfrom microorganisms.

The following lists typical industries and applications of compositions:

    ______________________________________                                        Industry      Application                                                     ______________________________________                                        Adhesives, sealants                                                                         adhesives                                                                     caulks                                                                        sealants                                                        Agriculture/food chain                                                                      adjuvant preservation                                                         agricultural active ingredient                                                agricultural chemical preservative                                            agricultural formulations preservation                                        animal feed preservation                                                      dairy chemicals                                                               fertilizer preservation                                                       food preservation                                                             food processing chemicals                                                     grain preservation                                                            post-harvest produce protection                                               sugar processing                                                              tobacco                                                         Construction products                                                                       asphalt/concrete                                                              cement modifiers                                                              construction products                                                         roof mastics                                                                  synthetic stucco                                                              wall mastics                                                                  joint cement                                                    Cosmetics and toiletries                                                                    cosmetics                                                                     raw materials for cosmetics, toiletries                                       toiletries                                                      Disinfectants, antiseptics                                                                  antiseptic                                                                    disinfectant                                                    Emulsions, dispersions                                                                      aqueous dispersions                                                           dispersed pigments                                                            latex                                                                         photographic emulsions                                                        pigment slurries                                                              polymer latices                                                 Formulated household                                                                        fabric softeners                                                products      polishes                                                                      waxes                                                                         hand dish detergents                                                          raw materials                                                                 liquid detergents                                                             hand soaps                                                      Industrial processing,                                                                      electrodeposition paint, baths, rinses.                         misc          electrodeposition pre-treatment, post                                         rinses                                                                        industrial fluids preservation                                                pasteurization baths                                                          process aid preservation                                        Industrial water treat-                                                                     cooling towers                                                  ment air washers                                                                            cooling water                                                                 water cooling                                                                 preservation/treatment of wooden                                              cooling tower slats and structural                                            members                                                                       can warmers                                                                   brewery pasteurization                                                        closed loop water cooling systems                               Laundry       household laundry products                                                    laundered goods                                                               laundry rinse water                                                           sanitizers-laundry                                              Leather, leather                                                                            leather and hide                                                products      leather and hide products                                       Lubricants, hydraulic                                                                       automotive lubricants and fluids                                aids          conveyor lubricants                                                           greases                                                                       hydraulic fluids                                                              lubricants                                                      Medical devices                                                                             diagnostic enzymes                                                            diagnostic kits                                                               medical devices                                                 Metalworking & related                                                                      cutting fluids                                                  app's         metal cleaning                                                                metalworking fluids                                             Odor control (active                                                                        air conditioning                                                ingredient)   animal bedding                                                                cat litter                                                                    chemical tiolet prep'ns                                                       deodorizers                                                                   humidifiers                                                                   industrial deodorants                                                         sanitary formulations                                                         toilet bowls                                                    Paints and coatings                                                                         emulsions                                                                     paints                                                          Paper and wood pulp,                                                                        absorbant materials of paper and wood                           their products                                                                              pulp                                                                          packaging materials of paper and wood                                         pulp                                                                          paper                                                                         paper products                                                                paper treatment                                                               soap wrap                                                                     wood pulp                                                                     wood pulp products                                              Paper mill    paper mill slimicides                                                         pulp and paper slurries                                         Petroleum refining, fuels                                                                   aviation fuels (jet fuel, aviation gas)                                       crude oils                                                                    burner, diesel and turbine fuel oils                                          coal slurries                                                                 diesel fuel additives                                                         diesel fuels                                                                  fuels                                                                         gasoline                                                                      heating oils                                                                  hydrocarbons                                                                  kerosene                                                                      liquefied petroleum gas                                                       petrochemical feedstocks                                                      petroleum products, storage,                                                  transportation and production                                                 recycled petroleum products                                                   residual fuel oils                                                            turbine oils                                                    Photographic Chemicals                                                                      photographic processing - wash water,                           and process   rinses                                                                        photoprocessing                                                               photoplate processing chemicals                                               (developers, stabilizers etc)                                   Printing      fountain solutions (printing)                                                 ink components (pigments, resins,                                             solvents, etc)                                                                inks                                                            Sanitizers (active)                                                                         sanitizers                                                                    sanitizers-dairy                                                              sanitizers-dental                                                             sanitizers-fermentation                                                       sanitizers-food preparation                                                   sanitizers-food processing                                                    sanitizers-medical                                                            sanitizers-rendering                                                          sanitizers-veterinary                                           Soaps, detergents,                                                                          cleaners                                                        cleaners      detergents                                                                    household cleaners                                                            industrial cleaners                                                           liquid soaps                                                                  oil and grease remover                                                        powdered soaps                                                                raw materials for cleaning products                                           soaps                                                                         surfactants                                                     Textiles, textile products                                                                  bonded fabrics                                                                burlap                                                                        canvas                                                                        canvas goods                                                                  carpet backing                                                                carpets                                                                       clothing                                                                      coated fabrics                                                                curtains                                                                      draperies                                                                     engineering textiles                                                          fibers                                                                        geotextiles                                                                   goods made of textiles                                                        knitted fabrics                                                               nets                                                                          nonwoven fabrics                                                              rope                                                                          rugs                                                                          textile accessories                                                           textile products                                                              textiles                                                                      upholstery                                                                    woven fabrics                                                                 yarn                                                            Textile processing                                                                          dye fixatives                                                                 dyes                                                                          fiber lubricants                                                              hand modifiers                                                                sizes                                                                         textile processing fluids                                       Therapeutic (active or                                                                      animal health/veterinary                                        preservative) aquaculture                                                                   dental                                                                        human health                                                                  pharmaceutical/therapeutic                                      Water purification                                                                          charcoal beds                                                                 deionization resins                                                           filters                                                                       membranes                                                                     reverse osmosis membranes                                                     ultrafilters                                                                  water purification                                                            water purification pipes, tubing                                Wood applications                                                                           lazures (wood stains)                                                         wood                                                                          wood products                                                   Miscellaneous alcohols                                                                      bedding incorporating water or gels                                           ceramic                                                                       contact lens cases-leaching                                                   electronic circuitry                                                          electronics chemicals                                                         enzymes-food production                                                       enzymes                                                                       enzymes-industrial                                                            gel cushions                                                                  marine antifoulants                                                           mildewcides                                                                   wood                                                                          plastics                                                                      laundry                                                                       mining                                                                        natural rubber latex                                                          oil field injection waters including                                          enhanced recover injection fluids,                                            drilling, fracturing and completion                                           fluids                                                                        pipes                                                                         plastics                                                                      polymer systems                                                               polymers and resins (synthetic and                                            natural)                                                                      reagent preservation                                                          rubber                                                                        rubber products                                                               skin remover                                                                  solid protective/decorative films                                             stains                                                                        swimming pools                                                                waste treatment                                                               water beds                                                      ______________________________________                                    

Because isothiazolones are so active as microbicides and only low levelsof hydrazide-containing compounds are required to achieve stabilization,the amount of hydrazide-containing compound in systems being treatedwill be very small, and therefore it is not likely to interfere withother components in systems requiring protection or with systems towhich the protected systems will be applied. Potential areas of generalapplication include metal-working fluids, cooling water, and airwashers.

One significant area of application for the compositions of theinvention is as microbicides in metal working fluids. Metal workingfluids are proprietary combinations of chemicals, which may contain,inter alia, ingredients such as alkanolamines, petroleum sulfonatesurfactants, oils (naphthenic, paraffinic, etc.), chlorinated paraffinsand fatty esters, sulfurized fatty compounds, phosphate esters, fattyacids and their amine salts, glycols, polyglycols, boric acid esters andamides. They are utilized in the milling, machining, drilling, and otherprocessing technologies for fabricating metal for the purposes oflubricating, cooling, preventing surface corrosion, and the like. Theyare sold in the form of active metal working fluids (MWF) concentrate,and are diluted in use to 1-10% active ingredients in water.

Because metal working fluids are recycled and stored, the growth ofmicroorganisms is favored. Isothiazolones have been found effective inpreventing the growth of such organisms. Certain of the components inthe metal working fluids will tend to destroy the isothiazolone and soremove its microbicidal protective activity, so that stabilizers for theisothiazolone against such degradation are desirable.

It is known in the art that the performance of microbicides may beenhanced by combination with one or more other microbicides. Thus, otherknown microbicides may be combined advantageously with the compositionof this invention.

The following examples are intended to illustrate the present inventionand not to limit it except as it is limited by the claims. Allpercentages are by weight unless otherwise specified, and all reagentsare of good commercial quality unless otherwise specified. Methods forquantitative determination of the isothiazolones in the followingexamples in metal-working fluids are described in detail in "Kathon® 886MW Microbicide and Kathon® 893 MW Fungicide: Analysis in MetalworkingFluids by High-Performance Liquid Chromatography", 1988, Rohm and HaasCompany.

EXAMPLES Example 1

These examples demonstrate the stabilizing effect ofhydrazide-containing compounds for isothiazolones added to metal workingfluids (MWF). MWF concentrate A was a "semi-synthetic" type having about10 to 15 percent naphthenic/paraffinic oil, about 50 percent water,emulsifying agents, pH adjusting amines, anticorrosive agents, and EP(extreme pressure) agents.

MWF concentrate B was an emulsifiable oil having about 30 to 50 percentoil, emulsifying agents, amines, anticorrosive agents, and EP agents.Into a glass vial in the following order were placed: a) 5 parts byweight of the MWF concentrate solution, b) 5 parts of the stabilizer insolution or dispersion, c) 5 parts water, d) 5 parts of an aqueoussolution containing 80 ppm active ingredient (AI), prepared by dilutionof a 14.4% aqueous solution of an approximately 75/25 mixture of5-chloro-2-methyl-3-isothiazolone and 2-methyl-3-isothiazolone, theformer being considered the active ingredient for these purposes; alsopresent was 9.2 weight percent magnesium chloride and 15.7% magnesiumnitrate. Thus the final mixture contained 3-5% of the MWF concentrate,20 ppm active ingredient of the isothiazolone, and 0 (control) to 1,000ppm of the stabilizer.

The vials were then capped, stored at ambient room temperature in aclosed cabinet for a designated time, filtered through a 0.45 micronfilter into another vial and analyzed the same day. The relativeconcentration of the active ingredient was determined by reverse phasehigh pressure liquid chromatography, utilizing a Varian model 5500chromatograph and an ultraviolet detector.

                  TABLE 1                                                         ______________________________________                                        STABILIZATION OF                                                              5-CHLORO-2-METHYL-3-ISOTHIAZOLONE IN MWF                                      CONCENTRATE A + B AFTER FOUR DAYS                                             Original system contained 15 ppm 5-chloro-2-methylisothiazolone               (Al) with 3% MWF Concentrate A and B in water. All                            stabilizers were added at 1000 ppm of solution.                                               % Al remaining                                                                  MWF A    MWF B                                              Stabilizer        Test #1  Test #2                                            ______________________________________                                        None              21       32                                                 α-Toluic hydrazide                                                                        51       --                                                 Maleic hydrazide  --       93                                                 ______________________________________                                    

While the invention has been described with reference to specificexamples and applications, other modifications and uses for theinvention will be apparent to those skilled in the art without departingfrom the spirit and scope of the invention defined in the appendedclaims.

We claim:
 1. A method of stabilizing 3-isothiazolone antimicrobialcompounds against chemical degradation in antagonistic environmentscomprising combining an amount of a second compound selected from thegroup consisting of hydrazides sufficient to stabilize said3-isothiazolone compound.
 2. A method according to claim 1 wherein saidhydrazide is combined in a weight ratio to 3-isothiazolone of about 1:10to 100:1.
 3. A method according to claim 1 wherein said ratio is about1:1 to 20:1.
 4. A method according to claim 1 wherein said environmentis selected from the group consisting of metal working fluid, latexpaint, bulk latex, cosmetics, cooling towers and surfactants.
 5. Amethod according to claim 1 wherein said hydrazide is selected from thegroup consisting of unsubstituted or substituted alkyl hydrazides, arylhydrazides, semicarbazides, heterocyclic hydrazides, and alkyldihydrazides.
 6. A composition comprising a 3-isothiazoloneantimicrobial compound and an amount of a hydrazide compound tosufficient stabilize said 3-isothiazolone.
 7. A composition according toclaim 6 further including a composition antagonistic to said3-isothiazolone selected from the group consisting of working fluid,latex paint, bulk latex, cosmetic, cooling towers and surfactant.
 8. Acomposition according to claim 6 wherein the weight ratio of hydrazideto 3-isothiazolone is about 1:10 to 100:1.
 9. A composition according toclaim 7 wherein said ratio is about 1:1 to 20:1.
 10. A compositionaccording to claim 6 wherein said hydrazide is selected from the groupconsisting of unsubstituted or substituted alkyl hydrazides, arylhydrazides, semicarbazide, heterocyclic hydrazides, and alkyldihydrazides.
 11. A composition according to claim 6 wherein said3-isothiazolone is of the formula (I) ##STR3## wherein Y is anunsubstituted or substituted (C₁ -C₈) alkyl, an unsubstituted orsubstituted (C₃ -C₁₂) cycloalkyl, an unsubstituted orhalogen-substituted (C₂ -C₈) alkenyl or alkynyl, an unsubstituted orsubstituted (C₇ -C₁₀) aralkyl, or an unsubstituted or substituted aryl;and R and R¹ is each independently H, halogen or (C₁ -C₄) alkyl.
 12. Acomposition according to claim 6 wherein Y is selected from: (C₁-C₈)alkyl or (C₃ -C₁₂)cycloalkyl each optionally substituted with one ormore of hydroxy, halo, cyano, alkylamino, dialkylamine, arylamino,carboxy, carbalkoxy, alkoxy, aryloxy, alkylethio, arylthio, haloalkoxy,cycloalkylamino, carbamoxy, or isothiazolonyl; an unsubstituted orhalo-substituted (C₂ -C₈) alkenyl or alkynyl; a (C₇ -C₁₀)aralkyloptionally substituted with one or more of halogen, (C₁ -C₄)alkyl or (C₁-C₄)alkoxy; and an optionally substituted with one or more of halogen,nitro, (C₁ -C₄)alkyl-acylamino, carb(C₁ -C₄)alkoxy or sulfamyl.
 13. Acomposition according to claim 6 which additionally comprises a polyolsolvent.
 14. A process of inhibiting or preventing the growth ofbacteria, fungi, algae, or yeast at a locus comprising introducing acomposition according to claim 6 into or onto said locus in sufficientamount to inhibit or prevent such growth.